EP3904445B1 - Reifenkautschukzusammensetzung und reifen - Google Patents

Reifenkautschukzusammensetzung und reifen Download PDF

Info

Publication number
EP3904445B1
EP3904445B1 EP21164828.2A EP21164828A EP3904445B1 EP 3904445 B1 EP3904445 B1 EP 3904445B1 EP 21164828 A EP21164828 A EP 21164828A EP 3904445 B1 EP3904445 B1 EP 3904445B1
Authority
EP
European Patent Office
Prior art keywords
group
mass
styrene
aromatic vinyl
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP21164828.2A
Other languages
English (en)
French (fr)
Other versions
EP3904445A1 (de
Inventor
Shinji Ikejiri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Rubber Industries Ltd
Original Assignee
Sumitomo Rubber Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Rubber Industries Ltd filed Critical Sumitomo Rubber Industries Ltd
Publication of EP3904445A1 publication Critical patent/EP3904445A1/de
Application granted granted Critical
Publication of EP3904445B1 publication Critical patent/EP3904445B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to tire rubber compositions and tires including the tire rubber compositions.
  • EP 3552840 A1 discloses a rubber composition for tires containing, based on 100% by mass of a rubber component therein: 3-25% by mass of a component derived from an aromatic vinyl monomer; 0-15% by mass of a component derived from a butadiene monomer and having a vinyl configuration; 1-90% by mass of a component derived from a butadiene monomer and having a cis configuration; and 1-6% by mass of a component derived from an isoprene monomer and having a cis configuration.
  • US 2019/010313 A1 discloses a pneumatic tire formed from a rubber composition which includes: a rubber component; a plasticizer component; and a filler component.
  • EP 3456764 A1 discloses rubber composition for treads which contains a rubber component and a plasticizer.
  • the present invention has been made in view of the above circumstances and aims to provide tire rubber compositions having improved wet grip performance during high-speed running, as well as tires including the tire rubber compositions.
  • the present invention relates to tire rubber compositions, containing: at least one rubber component (A) including an isoprene-based rubber and a styrene-butadiene-based rubber; at least one C5 resin and/or C5/C9 resin (B); and at least one aromatic vinyl polymer (C).
  • A including an isoprene-based rubber and a styrene-butadiene-based rubber
  • C5 resin and/or C5/C9 resin B
  • C aromatic vinyl polymer
  • the aromatic vinyl polymer is at least one selected from the group consisting of aromatic vinyl thermoplastic elastomers, homopolymers of aromatic vinyl compounds, and copolymers of aromatic vinyl compounds and terpene compounds.
  • the aromatic vinyl polymer contains a styrene unit.
  • the styrene-butadiene-based rubber has a styrene content of 30% by mass or higher.
  • the rubber compositions contain 10 to 60 parts by mass of the at least one aromatic vinyl polymer per 100 parts by mass of the at least one rubber component.
  • the rubber compositions contain 10 to 60 parts by mass in total of the at least one C5 resin and/or C5/C9 resin per 100 parts by mass of the at least one rubber component.
  • the present invention also relates to tires, including a tread formed from any of the rubber compositions.
  • the tire rubber compositions of the present invention contain at least one rubber component (A) including an isoprene-based rubber and a styrene-butadiene-based rubber, at least one C5 resin and/or C5/C9 resin (B), and at least one aromatic vinyl polymer (C), wherein the aromatic vinyl polymer is at least one selected from the group consisting of aromatic vinyl thermoplastic elastomers, homopolymers of aromatic vinyl compounds, and copolymers of aromatic vinyl compounds and terpene compounds.
  • A including an isoprene-based rubber and a styrene-butadiene-based rubber
  • C5 resin and/or C5/C9 resin B
  • the aromatic vinyl polymer is at least one selected from the group consisting of aromatic vinyl thermoplastic elastomers, homopolymers of aromatic vinyl compounds, and copolymers of aromatic vinyl compounds and terpene compounds.
  • Such tire rubber compositions have improved wet grip performance during high-speed running.
  • the tire rubber compositions of the present invention contain at least one rubber component (A) including an isoprene-based rubber and a styrene-butadiene-based rubber, at least one C5 resin and/or C5/C9 resin (B), and at least one aromatic vinyl polymer (C).
  • A an isoprene-based rubber and a styrene-butadiene-based rubber
  • C5 resin and/or C5/C9 resin B
  • the tire rubber compositions provide excellent wet grip performance during high-speed running.
  • the isoprene-based rubber and styrene-butadiene-based rubber polymers may form pseudo-crosslinks with the aromatic vinyl polymer (e.g., styrene-based polymer) by intermolecular interaction, resulting in the rubber compound having increased elastic modulus.
  • the intermolecular distance may be increased to cancel the interaction, resulting in reduced elastic modulus.
  • the C5 resin and/or C5/C9 resin reduce the elastic modulus of the rubber compound in all the strain regions. Therefore, the elastic modulus in the low strain regions hardly changes, and only the elastic modulus in the high strain regions decreases.
  • the rubber compositions contain at least one rubber component (Component (A)) including an isoprene-based rubber and a styrene-butadiene-based rubber.
  • Component (A) including an isoprene-based rubber and a styrene-butadiene-based rubber.
  • isoprene-based rubber refers to a polymer containing isoprene as a structural unit in which the amount of the isoprene unit based on 100% by mass of the total structural units in the polymer is 95% by mass or more.
  • the amount of the isoprene unit is preferably 98% by mass or more and may be 100% by mass.
  • the amount of the isoprene-based rubber(s) based on 100% by mass of the rubber components in the rubber compositions is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more.
  • the upper limit of the amount is preferably 90% by mass or less, more preferably 75% by mass or less, still more preferably 65% by mass or less. When the amount is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the weight average molecular weight (Mw) of the isoprene-based rubbers is preferably 60,000 or more, more preferably 80,000 or more, still more preferably 100,000 or more.
  • the upper limit of the Mw is preferably 3,000,000 or less, more preferably 2,500,000 or less, still more preferably 2,000,000 or less. When the Mw is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • Examples of the isoprene-based rubbers include natural rubbers (NR), polyisoprene rubbers (IR), refined NR, modified NR, and modified IR.
  • the NR and IR may be those commonly used in the tire industry, such as: SIR20, RSS#3, and TSR20 for the NR; and IR2200 for the IR.
  • Examples of the refined NR include deproteinized natural rubbers (DPNR) and highly purified natural rubbers (UPNR).
  • Examples of the modified NR include epoxidized natural rubbers (ENR), hydrogenated natural rubbers (HNR), and grafted natural rubbers.
  • Examples of the modified IR include epoxidized polyisoprene rubbers, hydrogenated polyisoprene rubbers, and grafted polyisoprene rubbers. These may be used alone or in combinations of two or more.
  • styrene-butadiene-based rubber refers to a polymer containing styrene and butadiene as structural units in which the combined amount of the styrene and butadiene units based on 100% by mass of the total structural units in the polymer is 95% by mass or more.
  • the combined amount of the styrene and butadiene units is preferably 98% by mass or more and may be 100% by mass.
  • the amount of the styrene-butadiene-based rubber(s) based on 100% by mass of the rubber components in the rubber compositions is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 35% by mass or more, particularly preferably 45% by mass or more.
  • the upper limit of the amount is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less. When the amount is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the weight average molecular weight (Mw) of the styrene-butadiene-based rubbers is preferably 60,000 or more, more preferably 200,000 or more, still more preferably 300,000 or more, particularly preferably 350,000 or more.
  • the upper limit of the Mw is preferably 1,500,000 or less, more preferably 800,000 or less, still more preferably 600,000 or less, particularly preferably 450,000 or less. When the Mw is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the styrene content of the styrene-butadiene-based rubbers is preferably 15% by mass or higher, more preferably 20% by mass or higher, still more preferably 25% by mass or higher, further preferably 30% by mass or higher.
  • the styrene content is preferably 60% by mass or lower, more preferably 50% by mass or lower, still more preferably 40% by mass or lower.
  • the vinyl bond content of the styrene-butadiene-based rubbers is preferably 5% by mass or higher, more preferably 10% by mass or higher, still more preferably 20% by mass or higher, further preferably 25% by mass or higher.
  • the vinyl bond content is preferably 50% by mass or lower, more preferably 40% by mass or lower, still more preferably 35 by mass or lower.
  • the styrene-butadiene-based rubbers may be either non-oil extended styrene-butadiene-based rubbers or oil extended styrene-butadiene-based rubbers.
  • the styrene-butadiene-based rubbers may be either unmodified styrene-butadiene-based rubbers or modified styrene-butadiene-based rubbers.
  • Any modified styrene-butadiene-based rubber having a functional group interactive with a filler such as silica may be used.
  • examples include a chain end-modified styrene-butadiene-based rubber obtained by modifying at least one chain end of a styrene-butadiene-based rubber with a compound (modifier) having the functional group (i.e., a chain end-modified styrene-butadiene-based rubber terminated with the functional group), a backbone-modified styrene-butadiene-based rubber having the functional group in the backbone, a backbone- and chain end-modified styrene-butadiene-based rubber having the functional group in both the backbone and chain end (e.g., a backbone- and chain end-modified styrene-butadiene-based rubber in which the backbone has the functional group, and at least one chain end is modified with the modifier), and
  • Examples of the functional group include amino, amide, silyl, alkoxysilyl, isocyanate, imino, imidazole, urea, ether, carbonyl, oxycarbonyl, mercapto, sulfide, disulfide, sulfonyl, sulfinyl, thiocarbonyl, ammonium, imide, hydrazo, azo, diazo, carboxyl, nitrile, pyridyl, alkoxy, hydroxyl, oxy, and epoxy groups. These functional groups may have a substituent.
  • amino groups preferably amino groups whose hydrogen atom is replaced with a C1-C6 alkyl group
  • alkoxy groups preferably C1-C6 alkoxy groups
  • alkoxysilyl groups preferably C1-C6 alkoxysilyl groups
  • amido groups preferably amino groups whose hydrogen atom is replaced with a C1-C6 alkyl group
  • the styrene-butadiene-based rubbers may be SBR products manufactured or sold by Sumitomo Chemical Co., Ltd., JSR Corporation, Asahi Kasei Corporation, Zeon Corporation, etc.
  • Rubber components (Component (A)) other than the isoprene-based rubbers and styrene-butadiene-based rubbers which may be used include rubbers used in the tire field, such as polybutadiene rubbers (BR), acrylonitrilebutadiene rubbers (NBR), chloroprene rubbers (CR), and butyl rubbers (IIR).
  • BR polybutadiene rubbers
  • NBR acrylonitrilebutadiene rubbers
  • CR chloroprene rubbers
  • IIR butyl rubbers
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC) (GPC-8000 series available from Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M available from Tosoh Corporation) calibrated with polystyrene standards.
  • the vinyl bond content (1,2-butadiene unit content) can be determined by infrared absorption spectrometry.
  • the styrene content can be determined by 1 H-NMR analysis.
  • the rubber compositions contain at least one C5 resin and/or C5/C9 resin (Component B).
  • the C5 resins and C5/C9 resins may be solid or liquid, preferably solid, at room temperature (25°C).
  • C5 resin refers to a polymer containing a C5 hydrocarbon or a multimer (e.g., a dimer) thereof as a structural unit.
  • the C5 hydrocarbon or multimer thereof include isoprene, pentane, and cyclopentadiene.
  • Specific examples of the C5 resins include copolymers of isoprene and styrene.
  • Other examples of the C5 resins include aliphatic petroleum resins produced by (co)polymerization of C5 fractions obtained from naphtha cracking processes in the petrochemical industry.
  • the C5 fractions include olefinic hydrocarbons such as 1-pentene, 2-pentene, and 2-methyl-1-butene, and diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, and 1,3-pentadiene.
  • olefinic hydrocarbons such as 1-pentene, 2-pentene, and 2-methyl-1-butene
  • diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, and 1,3-pentadiene.
  • C5/C9 resins examples include mixtures of the above-described C5 resins and C9 resins.
  • C9 resin refers to a polymer containing a C9 hydrocarbon or a multimer (e.g., a dimer) thereof as a structural unit.
  • Examples of the C9 hydrocarbon or multimer (e.g., dimer) thereof include indene, methylstyrene, and vinyltoluene.
  • the C9 resins include solid polymers produced by (co)polymerization of C9 fractions in the presence of Friedel-Crafts catalysts or the like, such as copolymers mainly containing indene, copolymers mainly containing methylindene, copolymers mainly containing ⁇ methylstyrene, and copolymers mainly containing vinyltoluene.
  • the C5 resins are C5 aliphatic resins
  • the C9 resins are C9 alicyclic resins.
  • the combined amount of the C5 resins and the C5/C9 resins per 100 parts by mass of the rubber components is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more.
  • the combined amount is also preferably 60 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less.
  • good properties such as wet grip performance during high-speed running tend to be obtained.
  • elastic modulus can be sufficiently reduced by incorporating at least a predetermined amount of the resins, while rigidity can be ensured by adjusting the combined amount to not more than a predetermined amount.
  • the amount of the C5 resins or C5/C9 mixture resins alone is preferably in the same range as indicated above.
  • the softening point of the C5 resins and/or C5/C9 resins is preferably 30°C or higher, more preferably 60°C or higher, but is preferably 160°C or lower, more preferably 150°C or lower. When the softening point is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the softening point of the polymers is determined in accordance with JIS K 6220-1:2001 using a ring and ball softening point measuring apparatus and defined as the temperature at which the ball drops down.
  • the weight average molecular weight (Mw) of the C5 resins and/or C5/C9 resins is preferably 1000 or more, more preferably 2000 or more, still more preferably 2500 or more, but is preferably 5000 or less, more preferably 4000 or less, still more preferably 3500 or less.
  • Mw is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the number average molecular weight (Mn) of the C5 resins and/or C5/C9 resins is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, but is preferably 2000 or less, more preferably 1300 or less, still more preferably 1100 or less.
  • Mn is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the rubber compositions contain at least one aromatic vinyl polymer (Component (C)).
  • the aromatic vinyl polymer is at least one selected from the group consisting of aromatic vinyl thermoplastic elastomers, homopolymers of aromatic vinyl compounds, and copolymers of aromatic vinyl compounds and terpene compounds.
  • the aromatic vinyl polymers may be solid or liquid, preferably solid, at room temperature (25°C).
  • the aromatic vinyl polymers may be used alone or in combinations of two or more.
  • aromatic vinyl polymer refers to a polymer containing an aromatic vinyl compound structural unit (a structural unit derived from an aromatic vinyl compound (aromatic vinyl unit)).
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, and 2,4,6-trimethylstyrene. These may be used alone or in combinations of two or more. Styrene or ⁇ -methylstyrene is preferred, and styrene is more preferred.
  • the aromatic vinyl unit is preferably a styrene unit.
  • the aromatic vinyl polymers may suitably be aromatic vinyl thermoplastic elastomers (thermoplastic elastomers having an aromatic vinyl compound block).
  • aromatic vinyl thermoplastic elastomers include copolymers (block copolymers) including a hard segment serving as a crosslinking point and a soft segment having rubber elasticity.
  • Examples of the hard segment include polystyrene, polypropylene, polyester, polyamide, poly(vinyl chloride), and polyurethane.
  • Examples of the soft segment include vinyl-polydiene, polyisoprene, polybutadiene, polyethylene, polychloroprene, and poly 2,3-dimethylbutadiene. One or two or more of these may be used.
  • the aromatic vinyl thermoplastic elastomers preferably contain, in addition to an aromatic vinyl unit, a non-conjugated olefin unit.
  • non-conjugated olefin unit refers to a structural unit derived from a non-conjugated olefin.
  • examples of the non-conjugated olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. These may be used alone or in combinations of two or more. Ethylene, 1-butene, and 3-methyl-1-butene are preferred, and ethylene is more preferred.
  • the non-conjugated olefin unit in the aromatic vinyl thermoplastic elastomers may be produced by polymerizing a non-conjugated olefin such as ethylene, or by polymerizing a conjugated diene compound such as 1,3-butadine and hydrogenating the resulting conjugated diene unit.
  • the aromatic vinyl thermoplastic elastomers containing a non-conjugated olefin unit may be copolymers of a non-conjugated olefin and other monomers, or hydrogenated products of copolymers (hydrogenated copolymers) of a conjugated diene compound and other monomers.
  • the percentage of the aromatic vinyl compound unit of the aromatic vinyl thermoplastic elastomers is preferably 5% by mass or higher, more preferably 10% by mass or higher, still more preferably 15% by mass or higher, but is preferably 70% by mass or lower, more preferably 50% by mass or lower, still more preferably 40% by mass or lower, particularly preferably 30% by mass or lower. When the percentage is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the percentages of the aromatic vinyl compound unit and the non-conjugated olefin unit can be calculated from the results of 1 H-NMR analysis.
  • the aromatic vinyl thermoplastic elastomers are preferably styrene block-containing thermoplastic elastomers (styrene thermoplastic elastomers).
  • styrene thermoplastic elastomers include styrene-vinylisoprene-styrene triblock copolymers (SIS), styrene-isobutylene diblock copolymers (SIB), styrene-butadiene-styrene triblock copolymers (SBS), styrene-ethylene/butylene-styrene triblock copolymers (SEBS), styrene-ethylene/propylene-styrene triblock copolymers (SEPS), styrene-ethylene/ethylene/propylene-styrene triblock copolymers (SEEPS), styrene-butadiene/butylene-styrene triblock copolymers (SBBS), and styrene-ethylene-butadiene copolymers. These may be used alone or in combinations of two or more. Styrene-ethylene/
  • aromatic vinyl polymers include homopolymers of aromatic vinyl compounds (e.g., styrene) and copolymers of aromatic vinyl compounds (e.g., styrene) and additional monomers.
  • additional monomers include terpene compounds and ⁇ -methylstyrene. Among these, terpene compounds are preferred; in other words, copolymers of aromatic vinyl compounds and terpene compounds are preferred.
  • terpene compound refers to a hydrocarbon having a composition represented by (C 5 H 8 ) n or an oxygencontaining derivative thereof, each of which has a terpene backbone and is classified as a monoterpene (C 10 H 16 ), sesquiterpene (C 15 H 24 ), diterpene (C 20 H 32 ), or other terpenes.
  • terpene compounds examples include ⁇ -pinene, ⁇ -pinene, dipentene, limonene, myrcene, alloocimene, ocimene, ⁇ -phellandrene, ⁇ -terpinene, ⁇ -terpinene, terpinolene, 1,8-cineole, 1,4-cineole, ⁇ -terpineol, ⁇ -terpineol, and ⁇ -terpineol.
  • the softening point of the aromatic vinyl polymers is preferably 40°C or higher, more preferably 70°C or higher, still more preferably 90°C or higher, but is preferably 160°C or lower, more preferably 140°C or lower, still more preferably 130°C or lower.
  • the softening point is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the amount of the aromatic vinyl polymers per 100 parts by mass of the rubber components is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, but is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less.
  • the amount is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • a larger amount of the aromatic vinyl polymers is believed to lead to easier interaction, thereby being more effective in improving wet grip performance during high-speed running.
  • a polymer containing an isoprene unit as a structural unit corresponds to an isoprene-based rubber when it has an isoprene unit content of 95% by mass or higher based on 100% by mass of the total structural units in the polymer and also has a Mw of 5000 or more, while it corresponds to a C5 resin when it has an isoprene unit content of lower than 95% by mass or a Mw of less than 5000.
  • a polymer containing styrene and butadiene as structural units corresponds to a styrene-butadiene-based rubber when it has a combined content of styrene and butadiene units of 95% by mass or higher and also has a Mw of 5000 or more, while it corresponds to an aromatic vinyl polymer when it has a combined content of styrene and butadiene units of lower than 95% by mass or a Mw of less than 5000.
  • a polymer containing an aromatic vinyl unit (e.g., styrene unit) and a C5 hydrocarbon unit (e.g., isoprene unit) as structural units corresponds to an aromatic vinyl polymer, rather than a C5 resin.
  • a polymer containing an aromatic vinyl unit (e.g., styrene unit) and a C5 hydrocarbon multimer unit (e.g., terpene unit) as structural units corresponds to a C5 resin, rather than an aromatic vinyl polymer.
  • a polymer containing an aromatic vinyl unit and a C9 hydrocarbon and/or its multimer unit (e.g., indene unit) as structural units corresponds to a C9 resin, rather than an aromatic vinyl polymer.
  • such polymers e.g., polymers having an isoprene unit content of 95% by mass or higher and a Mw of 5000 or more, polymers having a combined content of styrene and butadiene units of 95% by mass or higher and a Mw of 5000 or more
  • the aromatic vinyl polymers may be commercially available from Asahi Kasei Corporation, Yasuhara Chemical Co., Ltd., etc.
  • the rubber compositions may contain at least one resin other than the C5 resins, C5/C9 resins, and aromatic vinyl polymers which is solid at room temperature (25°C) (solid resin).
  • Any solid resin generally used in the tire industry may be used, and examples include p-t-butylphenol acetylene resins and acrylic resins.
  • the rubber compositions preferably contain at least one silica as filler.
  • the silica include dry silica (anhydrous silica) and wet silica (hydrous silica).
  • Wet silica is preferred among these because it contains a large number of silanol groups.
  • Commercial products available from Degussa, Rhodia, Tosoh Silica Corporation, Solvay Japan, Tokuyama Corporation, etc. may be used. These may be used alone or in combinations of two or more.
  • the amount of the silica per 100 parts by mass of the rubber components is preferably 25 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more.
  • the upper limit of the amount is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less. When the amount is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the nitrogen adsorption specific surface area (N 2 SA) of the silica is preferably 70 m 2 /g or more, more preferably 140 m 2 /g or more, still more preferably 160 m 2 /g or more, particularly preferably 200 m 2 /g or more.
  • the upper limit of the N 2 SA of the silica is preferably 300 m 2 /g or less, more preferably 250 m 2 /g or less. When the N 2 SA is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the N 2 SA of the silica is measured by the BET method in accordance with ASTM D3037-93.
  • the percentage of the silica based on 100% by mass of the combined amount of the silica and carbon black in the rubber compositions is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more.
  • the rubber compositions contain silica, they preferably contain at least one silane coupling agent together with the silica.
  • silane coupling agent may be used, and examples include sulfide silane coupling agents such as bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)-tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(2-triethoxysilylethyl)trisulfide, bis(4-trimethoxysilylbutyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-
  • Examples of the mercapto silane coupling agents include silane coupling agents having mercapto groups and silane coupling agents having protected mercapto groups. These may be used alone or in combinations of two or more.
  • Suitable mercapto silane coupling agents include (i) silane coupling agents represented by the following formula (2-1); and (ii) silane coupling agents containing linking units A and B represented by the following formulas (2-2) and (2-3), respectively.
  • R 201 represents a hydrogen atom, a halogen atom, a branched or unbranched C1-C30 alkyl group, a branched or unbranched C2-C30 alkenyl group, a branched or unbranched C2-C30 alkynyl group, or the alkyl group in which a terminal hydrogen atom is replaced with a hydroxy or carboxyl group; and R 202 represents a branched or unbranched C1-C30 alkylene group, a branched or unbranched C2-C30 alkenylene group, or a branched or unbranched C2-C30 alkynylene group, provided that R 201 and R 202 may together form a cyclic structure.
  • R 102 , R 105 , R 106 , R 107 , and R 108 in formula (2-1) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a tolyl group, a xylyl group, a naph
  • Examples of linear alkylene groups that may be used as R 109 in formula (2-1) include a methylene group, an ethylene group, a n-propylene group, a n-butylene group, and a hexylene group.
  • Examples of branched alkylene groups that may be used as R 109 include an isopropylene group, an isobutylene group, and a 2-methylpropylene group.
  • silane coupling agents of formula (2-1) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-decano
  • silane coupling agents containing linking units A and B of formulas (2-2) and (2-3) are used, the increase in viscosity during processing can be reduced as compared to when using polysulfidosilanes such as bis(3-triethoxysilylpropyl)tetrasulfide. This is probably because, since the sulfide moiety of the linking unit A is a C-S-C bond, these silane coupling agents are thermally more stable than tetrasulfides and disulfides, and thus the Mooney viscosity is less likely to increase.
  • polysulfidosilanes such as bis(3-triethoxysilylpropyl)tetrasulfide.
  • the decrease in scorch time can be reduced as compared to when using mercaptosilanes such as 3-mercaptopropyltrimethoxysilane. This is probably because, though the linking unit B has a mercaptosilane structure, the -C 7 H 15 moiety of the linking unit A may cover the -SH group of the linking unit B to inhibit it from reacting with the polymers, and therefore scorching is less likely to occur.
  • the linking unit A content of the silane coupling agents having the above structure is preferably 30 mol% or higher, more preferably 50 mol% or higher, but is preferably 99 mol% or lower, more preferably 90 mol% or lower.
  • the linking unit B content is preferably 1 mol% or higher, more preferably 5 mol% or higher, still more preferably 10 mol% or higher, but is preferably 70 mol% or lower, more preferably 65 mol% or lower, still more preferably 55 mol% or lower.
  • the combined content of the linking units A and B is preferably 95 mol% or higher, more preferably 98 mol% or higher, particularly preferably 100 mol%.
  • the linking unit A or B content refers to the amount including the linking unit A or B present at the chain end of the silane coupling agent, if any.
  • the linking unit A or B is present at the chain end of the silane coupling agent, its form is not limited as long as it forms a unit corresponding to formula (2-2) representing the linking unit A or to formula (2-3) representing the linking unit B.
  • halogen atom for R 201 examples include chlorine, bromine, and fluorine.
  • Examples of the branched or unbranched C1-C30 alkyl group for R 201 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, and a decyl group.
  • the alkyl group preferably has 1 to 12 carbon atoms.
  • Examples of the branched or unbranched C2-C30 alkenyl group for R 201 include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, and a 1-octenyl group.
  • the alkenyl group preferably has 2 to 12 carbon atoms.
  • Examples of the branched or unbranched C2-C30 alkynyl group for R 201 include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group.
  • the alkynyl group preferably has 2 to 12 carbon atoms.
  • Examples of the branched or unbranched C1-C30 alkylene group for R 202 include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group.
  • the alkylene group preferably has 1 to 12 carbon atoms.
  • Examples of the branched or unbranched C2-C30 alkenylene group for R 202 include a vinylene group, a 1-propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, a 2-pentenylene group, a 1-hexenylene group, a 2-hexenylene group, and a 1-octenylene group.
  • the alkenylene group preferably has 2 to 12 carbon atoms.
  • Examples of the branched or unbranched C2-C30 alkynylene group for R 202 include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, and a dodecynylene group.
  • the alkynylene group preferably has 2 to 12 carbon atoms.
  • the total number of repetitions (xb + yb) consisting of the sum of the number of repetitions (xb) of the linking unit A and the number of repetitions (yb) of the linking unit B is preferably in the range of 3 to 300.
  • the - C 7 H 15 moiety of the linking unit A may cover the mercaptosilane of the linking unit B to reduce the decrease in scorch time while ensuring good reactivity with the silica and the rubber components.
  • silane coupling agents containing linking units A and B of formulas (2-2) and (2-3) include NXT-Z30, NXT-Z45, and NXT-Z60 all available from Momentive. These may be used alone or in combinations of two or more.
  • Suitable mercapto silane coupling agents include (iii) silane coupling agents represented by the following formula (2-4).
  • R 6 to R 8 may be the same as or different from one another and each represent a branched or unbranched C1-C12 alkyl group, a branched or unbranched C1-C12 alkoxy group, or the group: -O-(R 10 -O) z -R 11 where R 10 groups, the number of which is indicated by z, may be the same as or different from one another and each represent a branched or unbranched divalent C1-C30 hydrocarbon group, R 11 represents a branched or unbranched C1-C30 alkyl group, a branched or unbranched C2-C30 alkenyl group, a C6-C30 aryl group, or a C7-C30 aralkyl group, and z represents an integer of 1 to 30; and R 9 represents a branched or unbranched C1-C6 alkylene group.
  • R 6 to R 8 each represent a branched or unbranched C1-C12 alkyl group, a branched or unbranched C1-C12 alkoxy group, or the group: -O-(R 10 -O) z -R 11 .
  • at least one of R 6 to R 8 groups is the group: -O-(R 10 -O) z -R 11 .
  • More preferably, two of R 6 to R 8 groups are each the group: -O-(R 10 -O) z -R 11 and the other is a branched or unbranched C1-C12 alkoxy group.
  • alkyl group for R 6 to R 8 examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, and a nonyl group.
  • alkoxy group for R 6 to R 8 examples include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.
  • R 10 represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the hydrocarbon group include branched or unbranched C1-C30 alkylene groups, branched or unbranched C2-C30 alkenylene groups, branched or unbranched C2-C30 alkynylene groups, and C6-C30 arylene groups. Branched or unbranched C1-C30 alkylene groups are preferred among these.
  • Examples of the branched or unbranched C1-C30, preferably C1-C15, more preferably C1-C3, alkylene groups for R 10 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group.
  • alkenylene groups for R 10 include a vinylene group, a 1-propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, a 2-pentenylene group, a 1-hexenylene group, a 2-hexenylene group, and a 1-octenylene group.
  • Examples of the branched or unbranched C2-C30, preferably C2-C15, more preferably C2-C3, alkynylene groups for R 10 include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, and a dodecynylene group.
  • Examples of the C6-C30, preferably C6-C15, arylene groups for R 10 include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.
  • the symbol z represents an integer of 1 to 30, preferably of 2 to 20, more preferably of 3 to 7, still more preferably of 5 or 6.
  • R 11 represents a branched or unbranched C1-C30 alkyl group, a branched or unbranched C2-C30 alkenyl group, a C6-C30 aryl group, or a C7-C30 aralkyl group, preferably a branched or unbranched C1-C30 alkyl group.
  • Examples of the branched or unbranched C1-C30, preferably C3-C25, more preferably C10-C15, alkyl group for R 11 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and an octadecyl group.
  • Examples of the branched or unbranched C2-C30, preferably C3-C25, more preferably C10-C15, alkenyl group for R 11 include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 1-octenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and an octadecenyl group.
  • Examples of the C6-C30, preferably C10-C20, aryl group for R 11 include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.
  • Examples of the C7-C30, preferably C10-C20, aralkyl group for R 11 include a benzyl group and a phenethyl group.
  • -O-(R 10 -O) z -R 11 include -O-(C 2 H 4 -O) 5 -C 11 H 23 , -O-(C 2 H 4 -O) 5 -C 12 H 25 , -O-(C 2 H 4 -O) 5 -C 13 H 27 , -O-(C 2 H 4 -O) 5 -C 14 H 29 , -O-(C 2 H 4 -O) 5 -C 15 H 31 , -O-(C 2 H 4 -O) 3 -C 13 H 27 , -O-(C 2 H 4 -O) 4 -C 13 H 27 , -O-(C 2 H 4 -O) 6 -C 13 H 27 , and -O-(C 2 H 4 -O) 7 -C 13 H 27 .
  • Examples of the branched or unbranched C1-C6, preferably C1-C5, alkylene group for R 9 include those described for the branched or unbranched C1-C30 alkylene groups for R 10 .
  • Examples of the compounds of formula (2-4) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and a compound represented by the formula below (Si363 available from Evonik-Degussa).
  • the compound of the formula below is suitable. These may be used alone or in combinations of two or more.
  • the amount of the silane coupling agents, if present, per 100 parts by mass of the silica is preferably 1 part by mass or more, more preferably 2 parts by mass or more, but is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.
  • the amount is not less than the lower limit, the effects such as improving dispersion tend to be sufficiently achieved.
  • the amount is not more than the upper limit, a sufficient coupling effect tends to be obtained, resulting in good reinforcing properties.
  • the rubber compositions may contain at least one carbon black as filler. Any carbon black may be used, and examples include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, and N762.
  • Commercial products available from Asahi Carbon Co., Ltd., Cabot Japan K.K., Tokai Carbon Co., Ltd., Mitsubishi Chemical Corporation, Lion Corporation, NSCC Carbon Co., Ltd., Columbia Carbon, etc. may be used. These may be used alone or in combinations of two or more.
  • the amount of the carbon black, if present, per 100 parts by mass of the rubber components is preferably 1 part by mass or more, more preferably 3 parts by mass or more, but is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.
  • the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably 50 m 2 /g or more, more preferably 80 m 2 /g or more, still more preferably 100 m 2 /g or more, but is preferably 200 m 2 /g or less, more preferably 150 m 2 /g or less, still more preferably 130 m 2 /g or less.
  • the nitrogen adsorption specific surface area of the carbon black is determined in accordance with JIS K6217-2:2001.
  • the combined amount of the silica and carbon black per 100 parts by mass of the rubber components in the rubber compositions is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, still more preferably 60 parts by mass or more.
  • the upper limit is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less.
  • the rubber compositions may contain at least one liquid plasticizer.
  • the liquid plasticizers may be any plasticizer that is liquid at 25°C, and examples include oils. These may be used alone or in combinations of two or more.
  • oils examples include process oils, vegetable oils, and mixtures thereof.
  • process oils include paraffinic process oils, aromatic process oils, and naphthenic process oils.
  • vegetable oils include castor oil, cotton seed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, rosin, pine oil, pine tar, tall oil, corn oil, rice oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, and tung oil.
  • the rubber compositions may contain at least one sulfur.
  • sulfur examples include those commonly used in the rubber industry, such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, and soluble sulfur.
  • Commercial products available from Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemicals Corporation, Flexsys, Nippon Kanryu Industry Co., Ltd., Hosoi Chemical Industry Co., Ltd., etc. may be used. These may be used alone or in combinations of two or more.
  • the amount of the sulfur per 100 parts by mass of the rubber components is preferably 0.5 parts by mass or more, more preferably 1.5 parts by mass or more, but is preferably 6 parts by mass or less, more preferably 4 parts by mass or less. When the amount is within the range indicated above, good properties such as wet grip performance during high-speed running tend to be obtained.
  • the rubber compositions may contain at least one vulcanization accelerator.
  • vulcanization accelerators examples include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide; thiuram vulcanization accelerators such as tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), and tetrakis(2-ethylhexyl)thiuram disulfide (TOT-N); sulfenamide vulcanization accelerators such as N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-oxyethylene-2-benzothiazole sulfenamide, and N,N'-diisopropyl-2-benzothiazole sulfenamide; and guanidine vulcanization accelerators such as diphenylguanidine, di
  • the rubber compositions may contain at least one zinc oxide.
  • the zinc oxide may be a conventional one.
  • Commercial products available from Mitsui Mining & Smelting Co., Ltd., Toho Zinc Co., Ltd., HakusuiTech Co., Ltd., Seido Chemical Industry Co., Ltd., Sakai Chemical Industry Co., Ltd., etc. may be used. These may be used alone or in combinations of two or more.
  • the amount of the zinc oxide per 100 parts by mass of the rubber components is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, but is preferably 8 parts by mass or less, more preferably 6 parts by mass or less.
  • the rubber compositions may contain at least one wax.
  • Any wax may be used, and examples include petroleum waxes such as paraffin waxes and microcrystalline waxes; naturally-occurring waxes such as plant waxes and animal waxes; and synthetic waxes such as polymers of ethylene, propylene, or other similar monomers.
  • Commercial products available from Ouchi Shinko Chemical Industrial Co., Ltd., Nippon Seiro Co., Ltd., Seiko Chemical Co., Ltd., etc. may be used. These may be used alone or in combinations of two or more.
  • the amount of the waxes per 100 parts by mass of the rubber components is preferably 1 part by mass or more, more preferably 2 parts by mass or more, but is preferably 6 parts by mass or less, more preferably 4 parts by mass or less.
  • the rubber compositions may contain at least one antioxidant.
  • antioxidants examples include naphthylamine antioxidants such as phenyl- ⁇ -naphthylamine; diphenylamine antioxidants such as octylated diphenylamine and 4,4'-bis( ⁇ , ⁇ '-dimethylbenzyl)diphenylamine; p-phenylenediamine antioxidants such as N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and N,N'-di-2-naphthyl-p-phenylenediamine; quinoline antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer; monophenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; and bis-, tris-, or polyphenolic antioxidants such as tetrakis[methylene-3
  • the amount of the antioxidants per 100 parts by mass of the rubber components is preferably 1 part by mass or more, more preferably 2 parts by mass or more, but is preferably 6 parts by mass or less, more preferably 4 parts by mass or less.
  • the rubber compositions may contain at least one stearic acid.
  • the stearic acid may be a conventional one. Commercial products available from NOF Corporation, Kao Corporation, FUJIFILM Wako Pure Chemical Corporation, Chiba Fatty Acid Co., Ltd., etc. may be used. These may be used alone or in combinations of two or more.
  • the amount of the stearic acid per 100 parts by mass of the rubber components is preferably 1 part by mass or more, more preferably 2 parts by mass or more, but is preferably 6 parts by mass or less, more preferably 4 parts by mass or less.
  • the rubber compositions may contain additives commonly used in the rubber industry, such as organic peroxides.
  • the amount of each of the additives is preferably 0.1 to 200 parts by mass per 100 parts by mass of the rubber components.
  • the rubber compositions may be prepared, for example, by kneading the above-described components using a rubber kneading machine such as an open roll mill or a Banbury mixer, and then vulcanizing the kneaded mixture.
  • a rubber kneading machine such as an open roll mill or a Banbury mixer
  • the kneading conditions are as follows.
  • the kneading temperature is usually 100 to 180°C, preferably 120 to 170°C.
  • the kneading temperature is usually 120°C or lower, preferably 85 to 110°C.
  • the composition obtained after kneading sulfur and vulcanization accelerators is usually vulcanized by press vulcanization, for example.
  • the vulcanization temperature is usually 140 to 190°C, preferably 150 to 185°C.
  • the vulcanization time is usually 5 to 15 minutes.
  • the rubber compositions are suitable for use in treads (cap treads) of tires, for example.
  • the tires (for example, pneumatic tires) of the present invention can be produced from the above-described rubber compositions by usual methods. Specifically, an unvulcanized rubber composition as described above may be extruded into the shape of a tire component such as a tread and then assembled with other tire components in a usual manner in a tire building machine to build an unvulcanized tire, which may then be heated and pressurized in a vulcanizer to produce a tire.
  • a tire component such as a tread
  • other tire components in a usual manner in a tire building machine to build an unvulcanized tire, which may then be heated and pressurized in a vulcanizer to produce a tire.
  • the tires can be used as tires for passenger vehicles, large passenger vehicles, large SUVs, heavy duty vehicles such as trucks and buses, light trucks, or motorcycles, racing tires (high performance tires), or other similar tires.
  • the tires may also be used as all-season tires, summer tires, winter tires (e.g., studless winter tires, cold weather tires), or other similar tires.
  • Rubber compositions of various formulations as shown in the table are prepared from the chemicals listed below on the assumption that they will be used in the tread of tires (tire size: 195/65R15). Then, the wet grip performance during high-speed running of these tires is calculated. The results are indicated in the "Evaluation" field of the table.
  • Styrene as an aromatic vinyl compound and cyclohexane are added to a sufficiently dried pressure resistant stainless steel reactor.
  • 1-benzyldimethylsilyl-3-methylindene [[1-(PhCH 2 )Me 2 Si]-3-Me]C 9 H 6 , a tris(bis(dimethylsilyl)amide)-gadolinium complex Gd[N(SiHMe 2 ) 2 ] 3 , and trimethylaluminum are charged into a glass vessel in a nitrogen atmosphere in a glove box, and toluene is then added to conduct a reaction at 80°C for six hours.
  • the catalyst solution is added to the pressure resistant stainless steel reactor and heated to 75°C.
  • ethylene as a non-conjugated olefin compound and then a toluene solution containing 5 g of 1,3-butadiene as a conjugated diene compound are introduced into the pressure resistant stainless steel reactor to conduct a polymerization reaction at 75°C for four hours in total.
  • the chemicals other than the sulfur and vulcanization accelerators in the formulation amounts shown in Table 1 are kneaded using a 1.7 L Banbury mixer (Kobe Steel, Ltd.) at 150°C for four minutes. Then, the sulfur and vulcanization accelerators are added, followed by kneading using an open roll mill at 80°C for five minutes to give an unvulcanized rubber composition.
  • the unvulcanized rubber composition is formed into the shape of a cap tread and assembled with other tire components, followed by vulcanization at 170°C for 15 minutes to prepare a test tire (tire size: 195/65R15).
  • the test tire is mounted on each wheel of a vehicle (a front-engine, front-wheel-drive domestic car with 2000 cc displacement).
  • the braking distance from an initial speed of 100 km/h on wet asphalt is determined to calculate the wet grip performance (braking distance) during high-speed running of the vehicle.
  • tire rubber compositions having improved wet grip performance during high-speed running, as well as tires including the tire rubber compositions. Included are tire rubber compositions containing at least one rubber component (A) including an isoprene-based rubber and a styrene-butadiene-based rubber, at least one C5 resin and/or C5/C9 resin (B), and at least one aromatic vinyl polymer (C).
  • A including an isoprene-based rubber and a styrene-butadiene-based rubber
  • C5 resin and/or C5/C9 resin B
  • aromatic vinyl polymer C

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

  1. Reifen, umfassend eine Lauffläche, die aus einer Kautschukzusammensetzung für Reifen gebildet ist, wobei die Kautschukzusammensetzung umfasst:
    zumindest einen Kautschukbestandteil (A), der einen Kautschuk auf Isoprenbasis und einen Kautschuk auf Styrol-Butadien-Basis beinhaltet;
    zumindest ein C5-Harz und/oder C5/C9-Harz (B); und
    zumindest ein aromatisches Vinylpolymer (C), wobei das aromatische Vinylpolymer zumindest eines ist, das aus der Gruppe ausgewählt ist, die aus thermoplastischen aromatischen Vinylelastomeren, Homopolymeren aus aromatischen Vinylverbindungen und Copolymeren aus aromatischen Vinylverbindungen und Terpenverbindungen besteht.
  2. Reifen nach Anspruch 1,
    wobei das aromatische Vinylpolymer eine Styroleinheit umfasst.
  3. Reifen nach Anspruch 1 oder 2,
    wobei der Kautschuk auf Styrol-Butadien-Basis einen Styrolgehalt von 30 Masse-% oder mehr aufweist.
  4. Reifen nach einem der Ansprüche 1 bis 3,
    wobei die Kautschukzusammensetzung 10 bis 60 Massenteile des zumindest einen aromatischen Vinylpolymers pro 100 Massenteile des zumindest einen Kautschukbestandteils umfasst.
  5. Reifen nach einem der Ansprüche 1 bis 4,
    wobei die Kautschukzusammensetzung 10 bis 60 Massenteile in Summe des zumindest einen C5-Harzes und/oder C5/C9-Harzes pro 100 Massenteile des zumindest einen Kautschukbestandteils umfasst.
EP21164828.2A 2020-04-13 2021-03-25 Reifenkautschukzusammensetzung und reifen Active EP3904445B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2020071868A JP7552062B2 (ja) 2020-04-13 2020-04-13 タイヤ用ゴム組成物及びタイヤ

Publications (2)

Publication Number Publication Date
EP3904445A1 EP3904445A1 (de) 2021-11-03
EP3904445B1 true EP3904445B1 (de) 2025-03-05

Family

ID=75426298

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21164828.2A Active EP3904445B1 (de) 2020-04-13 2021-03-25 Reifenkautschukzusammensetzung und reifen

Country Status (2)

Country Link
EP (1) EP3904445B1 (de)
JP (1) JP7552062B2 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7815685B2 (ja) * 2021-10-28 2026-02-18 住友ゴム工業株式会社 重荷重用タイヤ
JP7779098B2 (ja) * 2021-11-15 2025-12-03 住友ゴム工業株式会社 タイヤ用ゴム組成物及びタイヤ
JP7793129B2 (ja) 2022-02-03 2026-01-05 住友ゴム工業株式会社 空気入りタイヤ
JP2025122788A (ja) 2024-02-09 2025-08-22 住友ゴム工業株式会社 タイヤ

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4573369B2 (ja) 1998-11-26 2010-11-04 住友ゴム工業株式会社 タイヤトレッド用ゴム組成物
JP6173078B2 (ja) * 2013-07-08 2017-08-02 住友ゴム工業株式会社 タイヤ用ゴム組成物及び空気入りタイヤ
JP6953841B2 (ja) * 2017-07-05 2021-10-27 住友ゴム工業株式会社 空気入りタイヤ
JP6897397B2 (ja) * 2017-07-28 2021-06-30 住友ゴム工業株式会社 空気入りタイヤ
JP7077551B2 (ja) * 2017-09-13 2022-05-31 住友ゴム工業株式会社 タイヤ用ゴム組成物
WO2019117168A1 (ja) * 2017-12-14 2019-06-20 株式会社ブリヂストン ゴム組成物及びタイヤ
WO2019117217A1 (ja) * 2017-12-14 2019-06-20 株式会社ブリヂストン ゴム組成物およびタイヤ
JP6417064B1 (ja) * 2018-04-09 2018-10-31 住友ゴム工業株式会社 タイヤ用ゴム組成物及びタイヤ

Also Published As

Publication number Publication date
EP3904445A1 (de) 2021-11-03
JP7552062B2 (ja) 2024-09-18
JP2021167401A (ja) 2021-10-21

Similar Documents

Publication Publication Date Title
US11174375B2 (en) Tread rubber composition and pneumatic tire
EP3904445B1 (de) Reifenkautschukzusammensetzung und reifen
US11549007B2 (en) Copolymer, rubber composition, and tire
EP3878905B1 (de) Reifenlaufflächenzusammensetzung, reifenlauffläche und reifen für personenkraftwagen
EP3738997B1 (de) Motorradreifen
US20210347206A1 (en) Tread rubber composition and pneumatic tire
JP7756484B2 (ja) ゴム組成物及びタイヤ
EP3851488B1 (de) Reifenprofilkautschukzusammensetzung und luftreifen
JP7363102B2 (ja) 空気入りタイヤ
EP3808571B1 (de) Reifenzusammensetzung und reifen
JP7494496B2 (ja) タイヤ
JP7358776B2 (ja) タイヤ用ゴム組成物及び空気入りタイヤ
EP3705310A1 (de) Kautschukzusammensetzung für reifen sowie reifen
US12420588B2 (en) Tire
EP3907089B1 (de) Reifenprofilkautschukzusammensetzung und luftreifen
JP7686366B2 (ja) 加硫ゴム組成物及びタイヤ
EP3808569B1 (de) Reifenzusammensetzung und reifen
EP3825356B1 (de) Reifenkautschukzusammensetzung und reifen
EP3778751B1 (de) Kautschukzusammensetzung für reifen sowie luftreifen
JP7792745B2 (ja) タイヤ用組成物及びタイヤ
EP3825145A1 (de) Reifenkautschukzusammensetzung und reifen
JP7616244B2 (ja) トレッド用ゴム組成物及びタイヤ
EP4177072B1 (de) Reifengummizusammensetzung und luftreifen
JP7400206B2 (ja) ゴム組成物及びタイヤ
EP3868823A2 (de) Kautschukzusammensetzung und reifen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

B565 Issuance of search results under rule 164(2) epc

Effective date: 20211005

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20211119

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230510

REG Reference to a national code

Ref country code: DE

Free format text: PREVIOUS MAIN CLASS: C08L0007000000

Ipc: B60C0001000000

Ref country code: DE

Ref legal event code: R079

Ref document number: 602021026999

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C08L0007000000

Ipc: B60C0001000000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C08L 47/00 20060101ALI20241024BHEP

Ipc: C08L 25/06 20060101ALI20241024BHEP

Ipc: C08L 53/02 20060101ALI20241024BHEP

Ipc: C08L 57/02 20060101ALI20241024BHEP

Ipc: C08L 9/06 20060101ALI20241024BHEP

Ipc: C08L 7/00 20060101ALI20241024BHEP

Ipc: B60C 1/00 20060101AFI20241024BHEP

INTG Intention to grant announced

Effective date: 20241111

RIN1 Information on inventor provided before grant (corrected)

Inventor name: IKEJIRI, SHINJI

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602021026999

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250327

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20250417

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250429

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250606

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1772607

Country of ref document: AT

Kind code of ref document: T

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250707

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

REG Reference to a national code

Ref country code: CH

Ref legal event code: H13

Free format text: ST27 STATUS EVENT CODE: U-0-0-H10-H13 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20251024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250705

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250325

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602021026999

Country of ref document: DE

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20250331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250305

REG Reference to a national code

Ref country code: CH

Ref legal event code: L10

Free format text: ST27 STATUS EVENT CODE: U-0-0-L10-L00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250325

26N No opposition filed

Effective date: 20251208

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20250605